Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/62—Carbon oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
  • B01D53/864—Removing carbon monoxide or hydrocarbons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
  • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
  • B01J20/041—Oxides or hydroxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
  • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
  • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G3/00—Compounds of copper
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G3/00—Compounds of copper
  • C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
  • C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/40—Mixed oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/502—Carbon monoxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
  • B01D2257/708—Volatile organic compounds V.O.C.'s
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
  • B01J2220/42—Materials comprising a mixture of inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/50—Solid solutions
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

• the present invention relates to a new class of compounds having a gas-fixing activity, to a method for preparing said compounds, to methods for producing composite materials on various matrices and thin or thick films deposited on various substrates and containing said compounds, and to their use, as well as to a method for eliminating certain gases from a mixture that comprises them by using said compounds.
• type a) materials are compounds capable of eliminating water vapor from a mixture of gases, for example calcium sulfate, phosphorus pentoxide, magnesium chloride, or carbon dioxide from a mixture of gases, for example sodium and potassium hydroxides and calcium, strontium, and barium oxides.
• type b) fixing materials are materials having an activated surface, such as activated charcoal or the various types of zeolite or some kinds of clay.
• the fixing properties of type a) materials are selective, in that a compound is capable of fixing a single type of gas.
• the range of usable spontaneous reactions is rather limited and does not include gases which are highly harmful to the health and to the environment, such as nitrogen monoxide NO and carbon monoxide CO.
• the involved reactions may be irreversible, so that the fixer loses all activity after a given utilization cycle.
• type b) materials are not selective and fix gas molecules according to their size, degree of polarity, and relative molecular mass. These materials are unable to fix light molecules, such as the combustion products that are most harmful to the health and to the environment, such as mixtures of nitrogen oxides NO and N0 2 and carbon oxides, particularly the monoxide CO. Disclosure of the Invention
• a principal aim of the present invention is to eliminate the drawbacks of conventional materials having gas-fixing capabilities, with particular interest for the removal of noxious components from combustion products and more generally from gas mixtures.
• A is an alkaline-earth metal, an alkaline metal, a lanthanide or a solid solution thereof;
• B is a transition metal, an element of group III, or a solid solution thereof; and
• d has a value between 0 and 1.
• A is chosen from the group constituted by barium, cesium, potassium, strontium, a lanthanide, or solid solutions thereof.
• B is chosen from the group constituted by copper, nickel, manganese, iron, palladium, titanium, aluminum, gallium, zinc, cobalt, or solid solutions thereof.
• Examples of compounds according to the invention, wherein A is a solid solution of the above-mentioned cations, are those having the formula (Ba 2 _ ⁇ Sr ⁇ )Cu 3 0 6 produced with values of x up to 0.75.
• Other examples of compounds according to the invention, wherein B is a solid solution of the above ⁇ mentioned cations, have the formula
• Ba 2 (Cu 3 _ v .Pd v )0 (-j produced with y up to 0.33; Ba 2 (Cu 3 _ v Ni v )0 (;j produced with y up to 1.0.
• a compound having the formula Ba 2 Cu 3 0 5+ ⁇ has been identified and partially described in the literature (see for example . Wong-Ng and L.P. Cook, Powder Diffraction, 9 (1994), p. 280-289 and the references listed therein) . However, the researchers who preceded the inventors of the present invention did not realize that they were in the presence of a new class of compounds having particular chemical activity characteristics.
• Compounds having the formula A 2 B 3°6 ⁇ d accor ⁇ Yng to the present invention can be prepared by direct reaction starting from mixtures containing oxide, peroxide, and nitrate precursors. These compounds lead to a characteristic X-ray powder diffraction profile, a typical example whereof, related to a sample of Ba 2 Cu 3 0 6+ _., is shown in figure 1 (CuK ⁇ radiation was used).
• the formation temperatures of the compounds according to the present invention are typically within the range of 300 to 950°C. The optimum values of course vary as a function of the cations being used.
• the method for preparing the compounds having the formula A 2 B 3 0 6 ⁇ cj according to the present invention comprises a stage for the heat treatment of mixtures of oxides, peroxides, or salts of the required cations in highly oxidizing conditions. For example, heating occurs in a controlled atmosphere that contains only oxygen, nitrogen, and inert gases.
• the compounds according to the present invention can be prepared as polycrystalline aggregates, as components in composite materials having various matrices, and in the form of thin or thick layers on various substrates.
• the compounds according to the present invention can be prepared starting from a mixture comprising one or more oxygenated compounds of an alkaline or alkaline-earth metal and one or more oxides of transition metals or elements of group III.
• the compounds according to the present invention can be prepared starting from a mixture comprising one or more nitrates of an alkaline-earth or alkaline metal and one or more nitrates of transition metals or of elements of group III.
• the mixture is homogenized by milling with a mechanical mill or manually with a mortar and pestle of agate or with another method for dry mixing or for mixing in the presence of appropriate liquids;
• the homogenized mixture is placed in an inert refractory container (alumina or the like) and is heated in a furnace under a stream of oxygen and inert gas (the partial pressure of the oxygen is typically > 0.2 bar, 1 cc/sec) at 580 ⁇ 650°C.
• an inert refractory container alumina or the like
• the partial pressure of the oxygen is typically > 0.2 bar, 1 cc/sec
• Steps A2, A3, and A4 are repeated until a compound is obtained which provides the X-ray diffraction pattern shown in figure 1, which characterizes the Ba 2 Cu 3 0 6+(-j phase.
• the final product is a composite material wherein the compound Ba 2 Cu 3 0 6 ⁇ d fills the microcavities of the porous substrate.
• the solution is used to wet the surface of a substrate of temperature-resistant, non-porous, inert material, constituted by polycrystalline Al 2 0 3 with a relative density of 99.9% (other examples of usable non- porous inert materials are quartz, porcelain, Inconel, oxidation-resistant alloys and metals, etcetera);
• Steps F2 and F3 are repeated until a thin deposition of nitrates of the desired thickness, for example approximately 10 ⁇ , is obtained; F5) Same as B4.
• the final product is a film of Ba 2 Cu 3 0 6+cj having a presettable thickness.
• the present invention relates to a method for eliminating certain gases from a gaseous mixture including them.
• the ability of the compounds according to the present invention to fix molecules of various gases directly from the gaseous state has been verified by direct measurements, such as thermogravimetry, analysis of the gases in the reaction atmosphere, or by indirect measurements, such as Raman and infrared spectroscopy.
• the compounds according to the present invention are particularly adapted for fixing oxides and halogens in the gaseous phase. Examples of such gases are N0 2 , C0 2 , S0 2 , NO, CO, F 2 , and Cl 2 .
• the way of fixing the gas depends on the type of gas and on the temperature and composition of the atmosphere in which the reaction occurs.
• the inventors of the present invention have observed for the first time in the compounds of the class to which the present invention relates fixing phenomena which are intermediate between the behavior observed in conventional fixing compounds of types a) and b) described above.
• the gas molecules are in fact fixed by reacting chemically with the fixing material, in that they are bonded to the structure of the solid in the form of anions.
• the chemical reactions related to the fixing processes although continuously modifying the composition of the fixer, do not cause, over a broad range in terms of amount of fixed gas, the destruction of the structure of the fixing solid, the structural parameters whereof vary to a very small extent and in any case continuously as a function of the amount of gas removed from the reaction atmosphere. If the process is continued beyond these limits, absorption can continue but it entails the destruction of the fixer structure and the formation of oxides or of the salts corresponding to the anions that form.
• the gases fixed by means of the mechanisms that are active in the first stages of the process, regardless of their nature, enter the compounds according to the invention in the form of oxyanions or halide ions.
• the structural characteristics of the fixing compounds vary continuously during this first part of the process, in the same way in which the structural characteristics of a solid solution vary as one of its components varies.
• the fixing process is reversible for many of the fixable gases; by varying the partial pressures and the temperature it is possible to desorb them fully or partially.
• Gaseous oxides with a low oxidation state NO and CO, for example
• N0 2 and C0 2 oxidation state
• the oxygen composition produced by the normal state of oxidation of the cations (Ba 2+ and Cu ) would be 5 atoms per unit of the formula (Ba 2 Cu 3 0 5 ), whilst accurate determinations of the oxygen content in samples prepared according to the previously described procedures show an oxygen content that is typically in the range of 5.5 to 6.1 atoms per unit of the formula. Accordingly, the fixing processes do not require the addition of external oxygen; however, their yield is increased by the presence of oxygen in the gas mixtures placed in contact with the fixing materials.
• the method according to the present invention for eliminating certain gases from a gaseous mixture that includes them consists in placing the gas mixture in contact with a compound having the formula A 2 B 3 0 6-) .
• cj in pure form or as a component of composite materials, in which A is an alkaline-earth metal, an alkaline metal, a lanthanide, or a solid solution thereof; B is a transiti o n metal, an element of group III, or a solid solution thereof; and d has a value between 0 and 1, at a temperature between the melting temperature of the compound to be fixed and 650°C.
• A is chosen from the group constituted by barium, cesium, potassium, strontium, or solid solutions thereof
• B is chosen from the group constituted by copper, nickel, manganese, iron, palladium, titanium, aluminum, gallium, zinc, cobalt, or solid solutions thereof.
• Example 1 N0 2 " ixing 3 grams of B a 2 ,;:u 3 0 6 ⁇ d Produced according to procedure B) are placed in a U-shaped tube wherein a stream of N ⁇ 2 (50%) and air is made to flow (90 cc/min flow, 20°C temperature).
• FIG. 2 shows a first U-shaped tube (1) and a second U-shaped tube (2) which are parallel-connected with respect to the stream of N0 2 and air; a layer of Ba 2 Cu 3°6 ⁇ d is present in the base of tube (1), whilst a layer of white material (for example cotton) is present in the base of tube (2).
• the gas changes color from orange (represented by stippling) to colorless as a consequence of its passage through the layer of Ba 2 Cu 3°6 + d' whilst in tube (2) it remains of the same orange color after passing through the white layer.
• the fixing activity persists for approximately 300 minutes.
• a weight increase was found which corresponded, within the measurement errors (5%), to the total conversion of the initial compound into copper and barium nitrate salts and to the fixing of 10 moles of gas per mole of fixer.
• Figure 3 shows the result of an NO concentration analysis by mass spectrometry on two gas streams (112 cc/ in) originating from a common source of a mixture of He+0.4%NO, one of which passes through a reactor brought to 350°C which contains 1 gram of Ba Cu 3 0 6 ⁇ cj compound produced according to procedure A) .
• This measurement points out different fixing processes with separate kinetics.
• the amount of gas fixed at saturation (2 hours) is 0.28 moles per mole of fixer.
• an electric sensor for gas concentration which comprises a compound having the formula A 2 B 3°6 ⁇ d* ⁇ ⁇ e inventors have in fact found that for the compounds according to the present invention, during the gas fixing process, the value of electrical resistivity increases in proportion to the amount of gas that is incorporated.
• the compound B a 2 Cu 3° 6 ⁇ d ⁇ - s a se ⁇ "i conc luctor with typical values of electrical resistance at room temperature on the order of 10-100 ohm/cm. In the case of the fixing of nitrogen or carbon oxides, this value is up to 4 orders of magnitude higher.
• Figure 4 plots the electrical resistance of a film produced according to procedure E) and exposed to a stream of N0 (50%) and air at room temperature.
• the present invention relates to optical gas concentration sensors which comprise a compound having the formula 2 B 3 ° 6+ d"
• the inventors of the present invention have found that the compounds having the formula A 2 3 ( - ) 6 + d snow considerable variations in their optical properties during the gas incorporation process. These variations become apparent as variations in the intensities of the characteristic modes in infrared and Raman spectra, with the appearance of new optical modes caused by the characteristic vibrations of the incorporated anions and with the appearance of characteristics which cannot be ascribed to the initial material or to the guest anions, such as for example a plurality of highly intense luminescence peaks which appear as a consequence of the incorporation of small amounts of carbon oxides. In addition to the variations in the measured spectra, macroscopic changes in color are observed as a consequence of the incorporation of small amounts of carbon oxides.
• the color of the Ba 2 Cu 3 0 6 ⁇ ( - ⁇ changes from the initial dark blue to black, whilst a color change is observed towards greenish pale blue as a consequence of the incorporation of large amounts of nitrogen oxides bel ow 170°C .

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Analytical Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Environmental & Geological Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Biomedical Technology (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Catalysts (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Separation Of Gases By Adsorption (AREA)
• Auxiliary Devices For And Details Of Packaging Control (AREA)
• Polymerisation Methods In General (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Pallets (AREA)
• Investigating Or Analysing Materials By Optical Means (AREA)
• Crystals, And After-Treatments Of Crystals (AREA)
• Treating Waste Gases (AREA)
• Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
• Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Priority Applications (11)

Applications Claiming Priority (2)

Publications (3)

Family

ID=11341096

Family Applications (1)

Country Status (16)

Cited By (3)

Families Citing this family (8)

Citations (4)

Family Cites Families (10)

• 1996
  • 1996-02-12 IT IT96BO000063A patent/IT1285562B1/it active IP Right Grant
• 1997
  • 1997-02-10 BR BR9707277A patent/BR9707277A/pt unknown
  • 1997-02-10 DK DK97903251T patent/DK0880394T3/da active
  • 1997-02-10 CN CN97192174A patent/CN1210474A/zh active Pending
  • 1997-02-10 AT AT97903251T patent/ATE211942T1/de not_active IP Right Cessation
  • 1997-02-10 EP EP97903251A patent/EP0880394B1/en not_active Expired - Lifetime
  • 1997-02-10 RU RU98117080/12A patent/RU98117080A/ru not_active Application Discontinuation
  • 1997-02-10 AU AU17683/97A patent/AU710506B2/en not_active Ceased
  • 1997-02-10 PL PL97328329A patent/PL328329A1/xx unknown
  • 1997-02-10 KR KR1019980706202A patent/KR19990082469A/ko not_active Application Discontinuation
  • 1997-02-10 DE DE69709623T patent/DE69709623T2/de not_active Expired - Fee Related
  • 1997-02-10 WO PCT/EP1997/000598 patent/WO1997028884A2/en not_active Application Discontinuation
  • 1997-02-10 PT PT97903251T patent/PT880394E/pt unknown
  • 1997-02-10 JP JP9528171A patent/JP2000505720A/ja active Pending
  • 1997-02-10 KR KR1019980706165A patent/KR19990082432A/ko not_active Application Discontinuation
  • 1997-02-10 ES ES97903251T patent/ES2169846T3/es not_active Expired - Lifetime
  • 1997-02-10 US US09/117,392 patent/US6379638B1/en not_active Expired - Fee Related

Patent Citations (4)

Also Published As

Similar Documents

Legal Events